US20240145761A1 - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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Publication number
US20240145761A1
US20240145761A1 US18/574,233 US202218574233A US2024145761A1 US 20240145761 A1 US20240145761 A1 US 20240145761A1 US 202218574233 A US202218574233 A US 202218574233A US 2024145761 A1 US2024145761 A1 US 2024145761A1
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negative electrode
current collector
electrode current
lithium
positive electrode
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Yohei Uchiyama
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a lithium secondary battery.
  • Nonaqueous electrolyte secondary batteries are used for ICT devices, such as personal computers and smart phones, cars, power storage systems, and other applications.
  • ICT devices such as personal computers and smart phones, cars, power storage systems, and other applications.
  • the nonaqueous electrolyte secondary batteries used for such applications further improvement in capacity has been required.
  • One known example of a high-capacity nonaqueous electrolyte secondary battery is a lithium ion battery.
  • a higher capacity of the lithium ion battery can be achieved by using, as a negative electrode active material, for example, graphite in combination with an alloy active material, such as a silicon compound.
  • the improvement in capacity of the lithium ion battery is approaching to the limit.
  • lithium metal secondary battery As a nonaqueous electrolyte secondary battery superior in capacity to the lithium ion battery, a lithium secondary battery (lithium metal secondary battery) is seen as promising.
  • lithium metal deposits at the negative electrode during charging, and the lithium metal dissolves in the nonaqueous electrolyte during discharging.
  • Patent Literature 1 discloses a nonaqueous electrolyte secondary battery including: a positive electrode having a positive electrode active material comprising a lithium-containing transition metal oxide; a negative electrode which has a negative electrode current collector and in which lithium metal deposits on the negative electrode current collector during charging; a separator disposed between the positive electrode and the negative electrode; and a nonaqueous electrolyte.
  • the molar ratio of the total amount of lithium that the positive electrode and the negative electrode have to the amount of transition metal contained in the positive electrode is 1.1 or less.
  • a space layer is present between the negative electrode and the separator, and the positive electrode capacity ⁇ (mAh/cm 2 ) per unit area of the positive electrode, and the average value X ( ⁇ m) of the thickness of the space layer satisfy 0.05 ⁇ /X ⁇ 0.2.
  • a rupture occurs in the negative electrode current collector during charging and discharging, leading to deterioration of cycle characteristics.
  • a lithium secondary battery including: a positive electrode containing a positive electrode active material capable of absorbing and releasing lithium ions; a negative electrode including a negative electrode current collector; a separator disposed between the positive electrode and the negative electrode; and a nonaqueous electrolyte having lithium ion conductivity, wherein at the negative electrode, lithium metal deposits during charging, and the lithium metal dissolves during discharging, an oxygen content in the negative electrode current collector is 50 ppm or less, and the negative electrode current collector has a breaking strength of 300 MPa or less and has a breaking elongation of 4% or more.
  • FIG. 1 A schematic longitudinal cross-sectional view of a lithium secondary battery according to an embodiment of the present disclosure.
  • FIG. 2 An enlarged cross-sectional view of a region II in FIG. 1 .
  • FIG. 3 An enlarged cross-sectional view of a region III in FIG. 1 .
  • Embodiments of the present disclosure relate to a lithium secondary battery (lithium metal secondary battery) in which lithium metal is used as a negative electrode active material. That is, a lithium secondary battery according to an embodiment of the present disclosure includes a positive electrode containing a positive electrode active material capable of absorbing and releasing lithium ions, a negative electrode including a negative electrode current collector, a separator disposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte having lithium ion conductivity. At the negative electrode, lithium metal deposits during charging, and the lithium metal dissolves during discharging.
  • 70% or more, for example, of the rated capacity develops through deposition and dissolution of lithium metal.
  • the migration of electrons at the negative electrode during charging and during discharging is mainly due to the deposition and the dissolution of lithium metal at the negative electrode.
  • 70 to 100% (e.g., 80 to 100%, 90 to 100%) of the migration of electrons (in other words, electric current) at the negative electrode during charging and during discharging is due to the deposition and the dissolution of lithium metal.
  • the negative electrode of the lithium secondary battery according to the present disclosure differs from the negative electrode of a battery in which the migration of electrons at the negative electrode during charging and during discharging is mainly due to absorption and release of lithium ions by a negative electrode active material (graphite etc.).
  • the negative electrode of a lithium secondary battery according to the present disclosure may not necessarily contain a negative electrode active material (graphite etc.) that absorbs and releases lithium ions.
  • the open circuit potential (OCV: open circuit voltage) of the negative electrode at full charge is, for example, 70 mV or less versus lithium metal (dissolution/deposition potential of lithium). Being at full charge refers to a state where, when the rated capacity of the battery is denoted by C, the battery is charged until a state of charge (SOC) of, for example, 0.98 ⁇ C or more is reached.
  • SOC state of charge
  • the open circuit potential (OCV: open circuit voltage) of the negative electrode at full charge can be measured by disassembling the battery in a fully charged state under an argon atmosphere to take out the negative electrode, and assembling it into a cell for measurement, using lithium metal as a counter electrode.
  • the nonaqueous electrolyte of the cell may be of the same composition as the electrolyte in the disassembled battery.
  • the expansion amount of the negative electrode tends to increase.
  • the “expansion of the negative electrode” means that the sum of the volumes of the negative electrode and the deposited lithium metal increases. Especially when lithium metal deposits in a dendritic form, the expansion amount further increases. This tends to generate a stress in the negative electrode.
  • the present inventor has conducted extensive studies on the cause of the rupture occurrence in the negative electrode current collector during charging and discharging. As a result, it was newly found that the negative electrode current collector becomes brittle with repeated charging and discharging, and the embrittlement of the negative electrode current collector, together with the stress generated in the negative electrode, cause a rupture in the negative electrode current collector.
  • a SEM observation of the ruptured portion of the negative electrode current collector led to the following new findings.
  • At the ruptured portion of the negative electrode current collector there was observed almost no deformation of crystal grains in the ductile direction when the negative electrode current collector stretched and broke, and almost no tapering deformation of the negative electrode current collector, and the ruptured portion showed a state of brittle fracture. Many grain boundary cracks were observed along the grain boundaries on the surface of the negative electrode current collector. The brittle fracture is considered to have occurred due to the grain boundary cracks.
  • the embrittlement (grain boundary cracks) of the negative electrode current collector is affected by some substance generated at the negative electrode.
  • the present inventor has further conducted intensive studies, with focuses on the amount of oxygen in the negative electrode current collector (e.g., copper foil), and newly found that when the amount of oxygen is small, the embrittlement of the negative electrode current collector can be suppressed.
  • the oxygen content in the negative electrode current collector is 50 ppm or less
  • the negative electrode current collector has a breaking strength (tensile strength) of 300 MPa or less
  • the negative electrode current collector has a breaking elongation of 4% or more.
  • the negative electrode current collector tends to become brittle. If the breaking strength of the negative electrode current collector is more than 300 MPa, the positive electrode shows an increased tendency to buckle and, as a result, may penetrate through the separator, to cause a short circuit. If the breaking elongation of the negative electrode current collector is less than 4%, having been unable to withstand the stress caused by the swelling of dendrites, the negative electrode current collector may rupture due to ductile fracture.
  • the aforementioned “oxygen content in the negative electrode current collector” means the oxygen content in a base material excluding an oxide layer covering the surface of the negative electrode current collector.
  • the aforementioned “breaking strength” and “breaking elongation” mean the breaking strength and the breaking elongation in the direction of rolling, respectively.
  • the oxygen content in the negative electrode current collector is 50 ppm or less, may be 30 ppm or less, and may be 15 ppm or less. Note that the oxygen content (ppm) in the negative electrode current collector is a content expressed as a mass ratio.
  • the breaking strength of the negative electrode current collector is 300 MPa or less, may be 250 MPa or less, and may be 200 MPa or less. In view of improving the reliability in battery manufacturing, the breaking strength of the negative electrode current collector may be 50 MPa or more. When the breaking strength of the negative electrode current collector is less than 50 MPa, a cut tends to occur during roll transfer, and the handling worsens considerably. With regard to the range of the breaking strength, the above upper and lower limits can be combined in any combination.
  • the breaking elongation of the negative electrode current collector is 4% or more, may be 5% or more, and may be 10% or more. In view of improving the reliability in battery manufacturing, the breaking elongation of the negative electrode current collector may be 50% or less. When the breaking elongation of the negative electrode current collector exceeds 50%, a deformation tends to occur during roll transfer, and the handling worsens considerably. With regard to the range of the breaking elongation, the above upper and lower limits can be combined in any combination.
  • the oxygen content in the negative electrode current collector can be determined by the following method.
  • the initial battery is disassembled to take out the negative electrode current collector, to obtain a sample.
  • the sample may be a negative electrode current collector used in the battery fabrication process.
  • the sample is washed with nitric acid (1+1) for 10 seconds, to remove the oxide layer on the sample surface. The above washing is repeated until the sample is reduced by 10 mass % or more.
  • the sample is washed with distilled water, alcohol, and acetone in this order.
  • the sample is dried with hot air and immediately analyzed by an inert gas fusion-infrared absorption method, to determine the oxygen content in the sample.
  • an oxygen-nitrogen simultaneous analyzer TC-336, available from LECO Corporation
  • the breaking strength (tensile strength) and breaking elongation of the negative electrode current collector are determined in accordance with JIS Z 2241 (method of tensile test for metallic materials). However, since the negative electrode current collector has low strength and is a thin foil, skilled techniques are required for the measurement of the breaking elongation, and it is desirable to have the measurement done by an institution with a proven track record.
  • the ratio Y/X of the thickness Y of the separator to the thickness X of the negative electrode current collector may be 2.5 or more, may be 3 or more, and may be 4 or more.
  • the Y/X is, for example, 5 or less.
  • the range of the Y/X the above upper and lower limits can be combined in any combination.
  • the thickness Y of the separator refers to a thickness of the separator before formed into an electrode group (before housing the electrode group in a battery case).
  • the Y is the total value of the thicknesses of the plurality of materials.
  • the Y is the maximum value of the thickness.
  • the region where the separator has the thickness Y (maximum value) has an area of, for example, 20% to 80% of the total area of the separator facing the negative electrode.
  • the thickness X of the negative electrode current collector is, for example, 5 ⁇ m or more and 30 ⁇ m or less.
  • the cycle characteristics improve significantly.
  • the separator when the Y/X satisfies 2.5 or more (when the separator has a thickness of 2.5 times or more as large as the thickness of the negative electrode current collector), the separator as above serves as a buffer to the expansion of the negative electrode (swelling of dendrites) during charging, to relax the stress generated at the negative electrode (negative electrode current collector).
  • the actions exerted when the negative electrode current collector satisfies the above (i) to (iii), of suppressing the embrittlement of the negative electrode current collector and of improving the resistance to the stress generated in the negative electrode are synergized with the relaxation action exerted when the Y/X is 2.5 or more, of relaxing the stress generated in the negative electrode current collector, to make remarkable the effect of improving the cycle characteristics.
  • the negative electrode current collector fails to satisfy the above (i) to (iii), due to an increased influence of the rupture occurrence in the negative electrode current collector, the effect exerted when Y/X is 2.5 or more of relaxing the stress generated in the negative electrode is hardly exhibited.
  • the thickness X of the negative electrode current collector can be determined by measuring the thickness at 10 randomly selected points of the negative electrode current collector using a scanning electron microscope (SEM), and calculating the average value thereof.
  • the thickness Y of the separator can also be determined in the same manner. When the separator has a plurality of regions with different thicknesses, the thickness is measured at 10 randomly selected points in the region having the maximum thickness, and the average value thereof is calculated.
  • the negative electrode includes a negative electrode current collector.
  • lithium metal deposits on the surface of the negative electrode during charging. More specifically, through charging, lithium ions contained in the nonaqueous electrolyte receive electrons on the negative electrode current collector to become lithium metal, which deposits on the surface of the negative electrode current collector. The lithium metal deposited on the surface of the negative electrode current collector dissolves as lithium ions in the nonaqueous electrolyte through discharging.
  • the lithium ions contained in the nonaqueous electrolyte may be either derived from a lithium salt added to the nonaqueous electrolyte or supplied from the positive electrode active material through charging, or both.
  • the negative electrode current collector is typically a foil (sheet) containing a metal (or alloy) material.
  • a rolled copper foil may be used or a rolled copper foil subjected to heat treatment in an inert atmosphere may be used for the negative electrode current collector.
  • the breaking strength, the breaking elongation, and the crystal grain size can be adjusted. In general, as a result of heat treatment, the crystal grain size tends to increase due to recrystallization, the strength tends to decrease, and the breaking elongation tends to improve.
  • the rolled copper foil may contain a very small amount of components other than copper (e.g., Ni, Cr, Fe, Zn, Sn, Ag, Pb, Bi, Cd, Hg, O, P, S, Se, Te, H, etc.).
  • the content of Cu in the rolled copper foil may be 99.9 mass % or more, and may be 99.96 mass % or more.
  • the material for the rolled copper foil may be, for example, oxygen-free copper (JIS H 3100, alloy number C1020).
  • a lithium metal sheet may be placed in advance on a surface of the negative electrode current collector before the initial charging.
  • the lithium metal sheet is formed by, for example, attaching, electrodepositing or vapor depositing lithium metal on a surface of the negative electrode current collector.
  • a negative electrode mixture layer may be formed on a surface of the negative electrode current collector. In this case, the negative electrode mixture layer is formed thin so that lithium metal can deposit at the negative electrode during charging.
  • the negative electrode mixture layer is formed by applying a negative electrode mixture slurry containing a negative electrode active material, such as graphite, onto a surface of the negative electrode current collector.
  • the thickness of the lithium metal sheet (or negative electrode mixture layer) is not particularly limited, and is, for example, 3 to 300 ⁇ m.
  • the lithium metal sheet (negative electrode mixture layer) may be formed on the surface of one side of the negative electrode current collector, or may be formed on both sides of the negative electrode current collector.
  • the surface of the negative electrode current collector may be smooth. This allows for uniform deposition of lithium metal derived from the positive electrode on the negative electrode current collector, during charging. Being smooth means that the maximum height roughness Rz of the negative electrode current collector is 20 ⁇ m or less. The maximum height roughness Rz of the negative electrode current collector may be 10 ⁇ m or less. The maximum height roughness Rz is measured in accordance with JIS B 0601:2013.
  • the positive electrode includes, for example, a positive electrode current collector and a positive electrode mixture layer supported on the positive electrode current collector.
  • the positive electrode mixture layer includes, for example, a positive electrode active material, a conductive material, and a binder.
  • the positive electrode mixture layer may be formed on only one side or on both sides of the positive electrode current collector.
  • the positive electrode is obtained by, for example, applying a positive electrode mixture slurry containing a positive electrode active material, a conductive material, and a binder, onto both sides of the positive electrode current collector, drying the applied films, followed by rolling.
  • the positive electrode active material is a material that absorbs and releases lithium ions.
  • a lithium-containing transition metal oxide for example, a lithium-containing transition metal oxide, a transition metal fluoride, a polyanion, a fluorinated polyanion, a transition metal sulfide, and the like can be used. Preferred among them is a lithium-containing transition metal oxide, in terms of its low production cost and high average discharge voltage.
  • Examples of the transition metal element contained in the lithium-containing transition metal oxide include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, W, etc.
  • the lithium-containing transition metal oxide may contain one kind of transition metal element, or may contain two or more kinds of transition metal elements.
  • the transition metal element may be Co, Ni and/or Mn.
  • the lithium-containing transition metal oxide can contain one or more kinds of typical elements, as necessary. Examples of the typical element include Mg, Al, Ca, Zn, Ga, Ge, Sn, Sb, Pb, Bi, etc.
  • the typical element may be Al etc.
  • the conductive material is, for example, a carbon material.
  • a carbon material carbon black, acetylene black, Ketjen black, carbon nanotubes, graphite, and the like can be used.
  • a fluorocarbon resin for example, a fluorocarbon resin, a polyacrylonitrile, a polyimide resin, an acrylic resin, a polyolefin resin, a rubbery polymer, and the like can be used.
  • the fluorocarbon resin include polytetrafluoroethylene, polyvinylidene fluoride, etc.
  • the positive electrode current collector a foil, a film, and the like are used.
  • a carbon material may be applied onto a surface of the positive electrode current collector.
  • the material of the positive electrode current collector may be, for example, a metal material including Al, Ti, Fe, and the like.
  • the metal material may be Al, an Al alloy, Ti, a Ti alloy, an Fe alloy, and the like.
  • the Fe alloy may be stainless steel (SUS).
  • the thickness of the positive electrode current collector is, without particular limitation, for example, 5 ⁇ m or more and 30 ⁇ m or less.
  • a porous sheet having ion permeability and electrically insulating properties is used.
  • the porous sheet for example, a microporous film, a woven fabric, a non-woven fabric, and the like can be used.
  • the material of the separator is not particularly limited, but may be a polymer material.
  • the polymer material is exemplified by an olefin resin, a polyamide resin, a cellulose, and the like.
  • the olefin resin include polyethylene, polypropylene, a copolymer of ethylene and propylene, etc.
  • the separator may contain an additive, as necessary. Examples of the additive include an inorganic filler etc.
  • the separator may be constituted of a plurality of layers differing in shape and/or composition.
  • the nonaqueous electrolyte having lithium ion conductivity contains, for example, a nonaqueous solvent, and a lithium salt dissolved in the nonaqueous solvent.
  • the nonaqueous electrolyte may be in the form of liquid, and may be in the form of gel.
  • the nonaqueous electrolyte in the form of liquid is prepared by dissolving a lithium salt in a nonaqueous solvent. When the lithium salt is dissolved in a nonaqueous solvent, lithium ions and anions are produced.
  • the nonaqueous electrolyte in the form of gel contains a lithium salt and a matrix polymer, or contains a lithium salt, a nonaqueous solvent, and a matrix polymer.
  • a matrix polymer for example, a polymer material that is gelled by absorbing a nonaqueous solvent is used. Examples of the polymer material include a fluorocarbon resin, an acrylic resin, a polyether resin, etc.
  • the lithium salt or anion may be any known one utilized for a nonaqueous electrolyte in a lithium secondary battery. Specific examples thereof include BF 4 ⁇ , ClO 4 ⁇ , PF 6 ⁇ , CF 3 SO 3 ⁇ , CF 3 CO 2 ⁇ , imide anions, an oxalate complex anion, etc.
  • the oxalate complex anion may contain boron and/or phosphorus.
  • Examples of the oxalate complex anion include bis(oxalate)borate anion, BF 2 (C 2 O 4 ) ⁇ , PF 4 (C 2 O 4 ) ⁇ , PF 2 (C 2 O 4 ) 2 ⁇ , etc.
  • the nonaqueous electrolyte may include one of these anions singly, or two or more kinds thereof.
  • the nonaqueous electrolyte preferably includes at least an oxalate complex anion.
  • the oxalate complex anion interacts with lithium, allowing for uniform deposition of lithium metal in the form of fine particles. Therefore, local deposition of lithium metal can be easily suppressed.
  • the oxalate complex anion may be combined with another anion.
  • the other anion may be, for example, PF 6 ⁇ and/or imide anions.
  • nonaqueous solvent ester compounds, ether compounds, nitrile compounds, amide compounds, and the like can be used. These compounds include a halogen-substituted derivative and the like.
  • the halogen-substituted derivative is exemplified by a fluoride and the like.
  • the nonaqueous electrolyte may contain these nonaqueous solvents singly, or in combination of two or more kinds.
  • the nonaqueous solvent may contain at least one ether compound as a major component.
  • the major component as used herein means the content of the at least one ether compound in the nonaqueous solvent being 50 mass % or more, which may be 80 mass % or more.
  • the content of the at least one ether compound in the nonaqueous solvent may be 95 mass % or less, and may be 100 mass % or less.
  • the range of the content of the at least one ether compound in the nonaqueous solvent the above upper and lower limits can be combined in any combination.
  • the ether compounds are excellent in stability (especially in reduction resistance), serve to suppress the formation of decomposed products on the negative electrode current collector surface, and presumably have little influence on the negative electrode current collector.
  • the negative electrode current collector that satisfies the above (i) to (iii)
  • the cycle characteristics improvement effect resulted from suppressing the embrittlement of the negative electrode current collector can be remarkably obtained.
  • the negative electrode current collector fails to satisfy the above (i) to (iii), due to an increased influence of the rupture occurrence in the negative electrode current collector, the effect by the ether compound is hardly exhibited.
  • a cyclic ether and a chain ether are exemplified.
  • the cyclic ether include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, etc.
  • chain ether examples include 1,2-dimethoxyethane, diethyl ether, ethyl vinyl ether, methylphenyl ether, benzylethyl ether, diphenyl ether, dibenzyl ether, 1,2-diethoxyethane, diethylene glycol dimethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, etc.
  • 1,2-dimethoxyethane and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether are preferred.
  • ester compound for example, a carbonic acid ester, a carboxylic acid ester, and the like are exemplified.
  • a cyclic carbonic acid ester include ethylene carbonate, propylene carbonate, etc.
  • a chain carbonic acid ester include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate, etc.
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • diethyl carbonate etc.
  • a cyclic carboxylic acid ester include ⁇ -butyrolactone, ⁇ -valerolactone, etc.
  • Examples of a chain carboxylic acid ester include ethyl acetate, methyl propionate, methyl fluoropropionate, etc.
  • the concentration of the lithium salt in the nonaqueous electrolyte is, for example, 0.5 mol/L or more and 3.5 mol/L or less.
  • the concentration of the anion in the nonaqueous electrolyte may be set to 0.5 mol/L or more and 3.5 mol/L or less.
  • the concentration of the oxalate complex anion in the nonaqueous electrolyte may be set to 0.05 mol/L or more and 1 mol/L or less.
  • the nonaqueous electrolyte may contain an additive.
  • the additive may form a surface film on the negative electrode. When the surface film derived from the additive is formed on the negative electrode, the dendrite formation and growth can be easily suppressed.
  • examples of such an additive include vinylene carbonate, fluoroethylene carbonate (FEC), vinyl ethyl carbonate (VEC), etc.
  • FIG. 1 is a schematic longitudinal cross-sectional view of an example of a lithium secondary battery according to an embodiment of the present disclosure.
  • FIG. 2 is an enlarged view of a portion (a portion including a positive electrode) within a region II in FIG. 1 .
  • FIG. 3 is an enlarged view of a portion (a portion including a negative electrode) within a region III in FIG. 1 . Note that each figure is a schematic illustration, and the ratio of the dimensions (e.g., thickness) and the like of the components may differ from the actual ones.
  • a lithium secondary battery 10 includes a cylindrical battery case, a wound electrode group 14 housed in the battery case, and a nonaqueous electrolyte (not shown).
  • the electrode group 14 is constituted by winding a belt-like positive electrode 11 and a belt-like negative electrode 12 , with a separator 13 interposed between the positive electrode 11 and the negative electrode 12 .
  • the negative electrode 12 is constituted of a negative electrode current collector.
  • the negative electrode 12 (negative electrode current collector) has a thickness of X and faces the separator 13 having a thickness Y. Note that the thickness Y in FIG. 3 refers to the thickness of the separator 13 before the electrode group 14 is housed in a case body 15 .
  • the negative electrode 12 is constituted only of the negative electrode current collector in the present embodiment, the negative electrode may be constituted by placing a lithium metal sheet in advance on the surface of the negative electrode current collector before the initial charging, or the negative electrode may be constituted by forming a negative electrode mixture layer on the surface of the negative electrode current collector.
  • the negative electrode 12 is electrically connected via a negative electrode lead 20 to the case body 15 that also serves as a negative electrode terminal.
  • One end of the negative electrode lead 20 is connected to the negative electrode 12 , for example, at its end in the longitudinal direction, and the other end is welded to the case body 15 on its inner bottom surface.
  • the positive electrode 11 includes a positive electrode current collector 30 and a positive electrode mixture layer 31 , and is electrically connected via a positive electrode lead 19 to a cap 26 that also serves as a positive electrode terminal.
  • One end of the positive electrode lead 19 is connected to the positive electrode 11 , for example, near its center in the longitudinal direction.
  • the positive electrode lead 19 extending from the positive electrode 11 passes through a through-hole (not shown) formed in an insulating plate 17 and extends to a filter 22 .
  • the other end of the positive electrode lead 19 is welded to the filter 22 on its surface facing the electrode group 14 .
  • the battery case includes the case body 15 which is a bottomed cylindrical metal container, and a sealing body 16 that seals the opening of the case body 15 .
  • a gasket 27 is placed between the case body 15 and the sealing body 16 , and this ensures the airtightness of the battery case.
  • insulating plates 17 and 18 are placed at both ends of the electrode group 14 in the winding axis direction, respectively.
  • the case body 15 has, for example, a step portion 21 formed by pressing the side wall of the case body 15 partially from outside.
  • the step portion 21 may be formed annularly on the side wall of the case body 15 along the circumferential direction of the case body 15 .
  • the sealing body 16 is supported on the step portion 21 on the side facing the opening.
  • the sealing body 16 includes the filter 22 , a lower valve body 23 , an insulating member 24 , an upper valve body 25 , and the cap 26 . In the sealing body 16 , these members are stacked in this order.
  • the sealing body 16 is fitted at the opening of the case body 15 , with the cap 26 positioned outside the case body 15 and the filter 22 positioned inside the case body 15 .
  • Each of the aforementioned members constituting the sealing body 16 has, for example, a disk shape or a ring shape.
  • the lower valve body 23 and the upper valve body 25 are connected to each other at their respective central portions, and the insulating member 24 is interposed between their respective peripheral portions.
  • the filter 22 and the lower valve body 23 are connected to each other at their respective peripheral portions.
  • the upper valve body 25 and the cap 26 are connected to each other at their respective peripheral portions. That is, the members except the insulating member 24 are electrically connected to each other.
  • the lower valve body 23 is provided with a vent hole (not shown). Therefore, when the internal pressure of the battery case rises due to abnormal heat generation or other events, the upper valve body 25 bulges toward the cap 26 and spaced away from the lower valve body 23 . This breaks the electrical connection between the lower valve body 23 and the upper valve body 25 . When the internal pressure further rises, the upper valve body 25 raptures, to let the gas escape though an aperture (not shown) formed in the cap 26 .
  • the illustrated example is a cylindrical lithium secondary battery, the present embodiment can be applied without limited thereto.
  • the shape of the lithium secondary battery may be selected according to its use and the like from a cylindrical shape and other various shapes, such as coin, prismatic, sheet, and flat shapes.
  • the illustrated example includes a wound electrode group constituted by winding a positive electrode and a negative electrode, with a separator interposed therebetween, the electrode group also may be in any form, and may be a stacked electrode group constituted by stacking a positive electrode and a negative electrode, with a separator interposed therebetween.
  • any known ones can be used without particular limitation.
  • the lithium secondary battery according to the present disclosure will be specifically described below with reference to Examples and Comparative Examples.
  • the present disclosure is not limited to the following Examples.
  • NCA lithium-containing transition metal oxide
  • AB acetylene black
  • PVdF polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • a rectangular negative electrode current collector (thickness X: 10 ⁇ m) having an oxygen content, a breaking strength, and a breaking elongation whose values are shown in Table 1 was prepared.
  • a lithium alloy foil (thickness 25 ⁇ m) was pressure-bonded to the negative electrode current collector in an inert gas atmosphere. A negative electrode was thus produced.
  • E1 to E5 in Table 1 a rolled copper foil was used as the negative electrode current collector.
  • a foil of oxygen-free copper JIS H 3100, alloy number C1020 was used, and the foil was heat-treated in an inert atmosphere.
  • an electrolytic copper foil was used in C4
  • a foil of tough pitch copper JIS H 3100, alloy number C1100
  • a foil of phosphorus deoxidized copper JIS H 3100, alloy number C1201
  • LiPF 6 and LiBF 2 (C 2 O 4 ) were dissolved at 1 mol/L and 0.1 mol/L, respectively, to prepare a liquid nonaqueous electrolyte.
  • Table 1 for an ether-based nonaqueous electrolyte, 1,2-dimethoxyethane and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether were used as the nonaqueous solvent.
  • dimethyl carbonate was used as the nonaqueous solvent.
  • a tab made of Al was attached to the positive electrode obtained above.
  • a tab made of Ni was attached to the negative electrode obtained above.
  • the separator used here was a polyethylene thin film, and the thickness Y of the separator was set to the values shown in Table 1.
  • the resultant electrode group was housed in a pouch-like package member formed of a laminate sheet including an Al layer, and the above nonaqueous electrolyte was injected into the package member housing the electrode group, and then, the package member was sealed, to complete a lithium secondary battery.
  • E1 to E5 are batteries of Examples 1 to 5
  • C1 to C4 are batteries of Comparative Examples 1 to 4.
  • a constant-current charging was performed at 10 mA until the voltage reached 4.1 V, and then, a constant-voltage charging was performed at 4.1 V until the current reached 1 mA.
  • a constant-current discharging was performed at 10 mA until the voltage reached 3 V.
  • E3 to E5 showed that in E4 to E5 in which the Y/X was 2.5 or more, the cycle characteristics were further improved than in E3 in which the Y/X was less than 2.5.
  • the oxygen content was 50 ppm or less
  • the breaking strength was 300 MPa or less
  • the breaking elongation was 4% or more
  • the nonaqueous electrolyte was common.
  • the lithium secondary battery of the present disclosure is applicable to electronic devices, such as cellular phones, smart phones, and tablet terminals, electric cars including hybrids and plug-in hybrids, home storage battery systems combined with a solar cell, and the like.

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